Spectral,structural and theoretical study of the effects of thiocyanato and dicyanamido ligands on the geometry of PbII complexes containing a triazinic ligand

Two lead(II) complexes of 5,6‐bis(furan‐2‐yl)‐3‐(pyridin‐2‐yl)‐1,2,4‐triazine (DFPT), namely one‐dimensional (1D) catena‐poly[[bis[5,6‐bis(furan‐2‐yl)‐3‐(pyridin‐2‐yl‐κN)‐1,2,4‐triazine‐κN²]lead(II)]‐di‐μ‐thiocyanato‐κ²N:S;κ²S:N], [Pb(NCS)₂(C₁₆H₁₀N₄O₂)₂]_n, 1 , and binuclear di‐μ‐dicyanamido‐κ²N¹:N⁵;κ²N⁵:N¹‐bis{[5,6‐bis(furan‐2‐yl)‐3‐(pyridin‐2‐yl‐κN)‐1,2,4‐triazine‐κN²](nitrato‐κ²O,O′)lead(II)}, [Pb₂(C₂N₃)₂(NO₃)₂(C₁₆H₁₀N₄O₂)₄], 2 , as well as DFPT itself, were prepared and identified by elemental analysis, FT–IR, ¹H NMR spectroscopy and single‐crystal X‐ray structural analyses. In the double‐chain 1D coordination polymer of 1 and the binuclear structure of 2 , the Pb atom has a hemidirected‐PbN₆S₂ and a rare holodirected‐PbN₆O₂ environment, respectively, with a distorted cubic geometry. All the coordination modes of dicyanamide ligands within lead complexes were studied using the Cambridge Structural Database (CSD) to compare them with the structures of 1 and 2 . In addition to hydrogen bonds, the crystal networks are stabilized by π–π stacking interactions between the triazine, furyl and pyridine aromatic rings. The most stable theoretical structures of the title compounds predicted by density functional theory (DFT) calculations were compared with the solid‐state results.     

Reaction of 2‐[(2‐aminoethyl)amino]ethanol with pyridine‐2‐carbaldehyde and complexation of the products with CuII and CdII along with docking studies

The reaction between 2‐[2‐(aminoethyl)amino]ethanol and pyridine‐2‐carbaldehyde in a 1:2 molar ratio affords a mixture containing 2‐({2‐[(pyridin‐2‐ylmethylidene)amino]ethyl}amino)ethanol (PMAE) and 2‐[2‐(pyridin‐2‐yl)oxazolidin‐3‐yl]‐N‐(pyridin‐2‐ylmethylidene)ethanamine (POPME). Treatment of this mixture with copper(II) chloride or cadmium(II) chloride gave trichlorido[(2‐hydroxyethyl)({2‐[(pyridin‐2‐ylmethylidene)amino]ethyl})azanium]copper(II) monohydrate, [Cu(C₁₀H₁₆N₃O)Cl₃]·H₂O or [Cu(HPMAE)Cl₃]·H₂O, 1 , and dichlorido{2‐[2‐(pyridin‐2‐yl)oxazolidin‐3‐yl]‐N‐(pyridin‐2‐ylmethylidene)ethanamine}cadmium(II), [CdCl₂(C₁₆H₁₈N₄O)] or [CdCl₂(POPME)], 2 , which were characterized by elemental analysis, FT–IR, Raman and ¹H NMR spectroscopy and single‐crystal X‐ray diffraction. PMAE is potentially a tetradentate N₃O‐donor ligand but coordinates to copper here as an N₂ donor. In the structure of 1 , the geometry around the Cu atom is distorted square pyramidal. In 2 , the Cd atom has a distorted octahedral geometry. In addition to the hydrogen bonds, there are π–π stacking interactions between the pyridine rings in the crystal packing of 1 and 2 . The ability of PMAE, POPME and 1 to interact with ten selected biomolecules (BRAF kinase, CatB, DNA gyrase, HDAC7, rHA, RNR, TrxR, TS, Top II and B‐DNA) was investigated by docking studies and compared with doxorubicin.     

Solvent-Free Crossed Aldol Condensation of Ketones with Aromatic Aldehydes Mediated by Magnesium Hydrogensulfate

Summary.  Crossed aldol condensations of ketones with aromatic aldehydes are carried out efficiently in the presence of magnesium hydrogensulfate under solvent-free conditions in good to excellent yield without the occurrence of any self-condensation. Similar reactions in solution do not proceed satisfactorily. Corresponding authors. E-mail: p-salehi@cc.sbu.ac.ir Received September 20, 2001. Accepted (revised) January 16, 2002     

Solvent-Free Crossed Aldol Condensation of Ketones with Aromatic Aldehydes Mediated by Magnesium Hydrogensulfate

 Crossed aldol condensations of ketones with aromatic aldehydes are carried out efficiently in the presence of magnesium hydrogensulfate under solvent-free conditions in good to excellent yield without the occurrence of any self-condensation. Similar reactions in solution do not proceed satisfactorily.     

A line search trust-region algorithm with nonmonotone adaptive radius for a system of nonlinear equations

In this paper, a trust-region procedure is proposed for the solution of nonlinear equations. The proposed approach takes advantages of an effective adaptive trust-region radius and a nonmonotone strategy by combining both of them appropriately. It is believed that selecting an appropriate adaptive radius based on a suitable nonmonotone strategy can improve the efficiency and robustness of the trust-region frameworks as well as decrease the computational cost of the algorithm by decreasing the required number subproblems that must be solved. The global convergence and the local Q-quadratic convergence rate of the proposed approach are proved. Preliminary numerical results of the proposed algorithm are also reported which indicate the promising behavior of the new procedure for solving the nonlinear system.     

An improved adaptive trust-region algorithm

This paper gives a variant trust-region method, where its radius is automatically adjusted by using the model information gathered at the current and preceding iterations. The primary aim is to decrease the number of function evaluations and solving subproblems, which increases the efficiency of the trust-region method. The next aim is to update the new radius for large-scale problems without imposing too much computational cost to the scheme. Global convergence to first-order stationary points is proved under classical assumptions. Preliminary numerical experiments on a set of test problems from the CUTEst collection show that the presented method is promising for solving unconstrained optimization problems.     

Back‐propagation artificial neural network and attenuated total reflectance‐Fourier transform infrared spectroscopy for diagnosis of basal cell carcinoma by blood sample analysis

A diagnostic method for the cancer, based on investigation of infrared spectra of blood samples, has been developed. The two‐layer modified principal component feed forward back‐propagation artificial neural network (BP‐ANN) was used to classify the attenuated total reflectance‐Fourier transform infrared (ATR‐FTIR) spectra of blood samples obtained from healthy people and those with basal cell carcinoma (BCC). Results showed 98.33% of accuracy, in comparison with the current clinical methods. In the first step, 20 blood samples (10 normal and 10 cancer cases) were applied to construct the calibration model. Spectroscopic studies were performed in 900–1800 cm⁻¹ spectral region with 3.85 cm⁻¹ data space. In order to modify the capability of ANN in prediction of test samples, two different algorithms were applied. The obtained results confirmed the compatibility of the proposed network with the architecture of 20‐8‐2 (input‐hidden‐output) with the pattern model. It was concluded that analysis of blood samples by ATR‐FTIR spectroscopy and ANN chemometric technique would be a reliable approach for detection of BCC. Copyright © 2009 John Wiley & Sons, Ltd.     

Electrodeposited Ni(OH)<Subscript>2</Subscript> nanostructures on electro-etched carbon fiber paper for highly stable supercapacitors

Herein, we introduce a facile, inexpensive and fast, and additive-/template-free method to fabricate highly stable nickel hydroxide nanofibers for supercapacitor applications. Ni(OH)₂ nanofibers were electrodeposited on electro-etched carbon fiber paper by a potential step method (Ni(OH)₂-ECFs) and characterized using scanning electron microscopy and X-ray diffraction analysis. Electrochemical performance of Ni(OH)₂-ECF was studied in symmetric two-electrode assembly by cyclic voltammetry, galvanostatic charge–discharge method, and electrochemical impedance spectroscopy. A specific capacitance of 277.5 F g^?1 was achieved for the symmetric supercapacitor based on two identical Ni(OH)₂-ECFs. Our findings demonstrate high-rate capability with excellent stability (approximately 100 % capacitance retention) for Ni(OH)₂-ECF supercapacitor, originated from the intimate contact between Ni(OH)₂ and ECF. Our studies suggest the Ni(OH)₂-ECF electrode as an excellent material for supercapacitor applications.     

Using experimental methods and CSD data for investigating the products of the reaction between 2-((2-aminoethyl)amino)ethanol with CdI2 and CdI2/HgI2-mixtures

The binding modes of 2-((2-aminoethyl)amino)ethanol-based ligands were explored using the Cambridge Structural Database (CSD). To extend this field, a new cadmium complex containing 2-((2-aminoethyl)amino)ethanol (AEAE), [Cd(AEAE)₂][Cd(AEAE)₂]′[CdI₄]₂ (1), was prepared and characterized by spectroscopic methods and single-crystal X-ray diffraction. The reaction of AEAE with a 1:1 mixture of CdI₂ and HgI₂ was also investigated. The complex, [Cd(AEAE)₂][I₂Hg(μ-I₂)₂HgI₂] (2), was synthesized and characterized. Compounds 1 and 2 represent the first tridentate binding modes of an AEAE type ligand with Cd²⁺. Geometrical investigation for complexes containing Cd(N^amine₂O^alcohol)₂, CdI_n, and HgI_n environment were carried out using the CSD software. Also different possible diastereomers which can be formed in coordination of a pair of tridentate AEAE ligands in octahedral geometry were studied and discussed.